Fluorine-Containing Dicarboxylic Acids and Their Novel Polymer Compounds

ABSTRACT

A fluorine-containing dicarboxylic acid represented by formula (1), 
     
       
         
         
             
             
         
       
     
     wherein n represents an integer of 1-4, and the two carboxylic groups are not adjacent to each other on the aromatic ring. It is possible to obtain a linear polymer compound by reacting the fluorine-containing dicarboxylic acid with a comonomer (e.g., diaminodiol). By thermal cyclization, this linear polymer compound can be converted into another polymer compound having superior characteristics.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of co-pending application Ser. No.12/174,414, filed Jul. 16, 2008, now U.S. Pat. No. ______. Priority isclaimed based on Japanese patent application no. 2007-185257, filed Jul.17, 2007, the entire disclosure of which is incorporated herein byreference.

BACKGROUND OF THE INVENTION

The present invention relates to novel fluorine-containing dicarboxylicacids and novel polymer compounds derived from the same.

Polyester, polyamide, polyimide, and polybenzoxazole have been developedas representatives of organic polymers having high heat resistance. Theyform a large market in electronic device field, engineering plasticfield for automobile and aerospace uses, etc., fuel cell field, medicalmaterial field, optical material field, etc. As their center, variousmany polymers have been put into practical uses, such as polyamidesrepresented by nylon and Kevlar, polyacrylates used for liquid crystalpolymers, polyimides represented by Kapton, and polybenzoxazolesrepresented by Zylon.

It is possible to produce polyester by a process by a polycondensationbetween dicarboxylic acid and diol in the presence of a condensing agentor by a process by converting dicarboxylic acid into an acid chloride orester, followed by a polycondensation with diol. It is possible toproduce polyamide by a process by a polycondensation betweendicarboxylic acid and diamine in the presence of a condensing agent orby a process by converting dicarboxylic acid into a carboxylic chlorideor ester, followed by a polycondensation with diamine. It is possible toproduce polyimide by polymerizing diamine with tetracarboxylicdianhydride, followed by a dehydration, ring-closing reaction. It ispossible to produce polybenzoxazole by a process by a polycondensationbetween dicarboxylic acid and bisaminophenol in the presence of acondensing agent and then a dehydration, ring-closing reaction.Alternatively, it may be conducted by converting dicarboxylic acid intoa carboxylic chloride or ester, then a polycondensation withbisaminophenol, and then a dehydration, ring-closing reaction.

In research and development of these resins, it has widely been tried tointroduce a hydroxy group(s), which is not directly involved in thepolymerization (polycondensation) and remains in the resin even afterthe polycondensation, into the monomer to provide the resin with afurther function(s). For example, in Japanese Patent ApplicationPublication 2003-268233 A (Patent Publication 1), a phenolic hydroxygroup is introduced as a photosensitive group for providing the resinwith alkali solubility. In Japanese Patent Application Publication2003-206352 A (Patent Publication 2), a phenolic hydroxy group isintroduced as an adhesive group for providing adhesion between fibersand a resin matrix in a composite material. In International PublicationWO 2007/010932 A1 or its corresponding Canadian Patent ApplicationPublication 2614648 A1 (Patent Publication 3), a phenolic hydroxy groupis introduced as a crosslinking point moiety.

The resin of Patent Publication 1 is described therein as apolybenzoxazole. To produce this polybenzoxazole, there is conducted apolycondensation between a bisaminophenol derivative (a polymerizablemonomer), in which an amino group and a phenolic hydroxy group areadjacent to each other, and a dicarboxylic acid, thereby firstlysynthesizing a polyamidephenol precursor containing phenolic hydroxygroups. The phenolic hydroxy group of this precursor serves as aphotosensitive group upon patterning by photolithography and thendisappears by the subsequent heating as the precursor is modified intoan oxazole ring of the final product.

In contrast, In Patent Publications 2 or 3, hydroxyl group is usedmainly as an adhesive group or crosslinking point moiety and partlyremains in the final product.

Recently, there have been active research and development in the fieldsof photoresist material and the like by using fluorine-containingcompounds, which are superior in transparency in ultraviolet region,particularly in vacuum ultraviolet region. In particular,fluorine-containing hydroxy compounds (fluorocarbinols) are often used.Fluorine is introduced as fluorocarbinol group to achieve adhesion tosubstrate, high glass transition point, photosensitivity, while allowingtransparency at each wavelength for use, due to acidity offluorocarbinol group, alkali development property, and the like. Offluorocarbinol group, particularly hexafluoroisopropanol moiety (i.e.,2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group) attracts muchattention due to its dissolution behavior, anti-swelling property, andhigh contrast, etc. Therefore, a lot of research and development isconducted (see Journal of Photopolymer Science and Technology, Volume17, No. 14 (2004) pp. 609-619 (Non-patent Publication 1) andInternational Publication WO 2006/070728 A1 or its correspondingEuropean Patent Application Publication EP 1832618 A1 (PatentPublication 4)).

Fluorine-containing compounds are under development and practical use inthe field of various materials, such as polyolefins and condensedpolymers, mainly in the field of advanced materials, due tocharacteristics of fluorine, such as water repellency, oil repellency,low water absorption, heat resistance, weather resistance, corrosionresistance, transparency, photosensitivity, low refractive index, andlow-dielectric constant. In the field of condensed polymers, there areproposals for introducing fluorine into diamine monomers, such as adiamine monomer containing a fluorine atom(s) or trifluoromethylgroup(s) substituted for a hydrogen(s) of its benzene ring, a diaminemonomer containing a hexafluoroisopropenyl group introduced between twoaromatic rings, and a fluorine-containing diamine monomer in which abenzene ring has been subjected to hydrogen reduction. Furthermore, abishydroxyamine monomer containing a hexafluoroisopropenyl group as acenter atomic group and aromatic hydroxyamines at its both sides is inpractical use. In this case, it is applied as polybenzoxazole orhydroxy-containing polyimide.

There are, however, few developments of heat resistant polymers (e.g.,polyester, polyamide, polyimide, and polybenzoxazole) containing ahexafluoroisopropanol moiety as acidic alcohol (see Patent Publication4, Japanese Patent Application Publication 2007-119503 or itscorresponding European Patent Application Publication EP 1783158 A1(Patent Publication 5), Japanese Patent Application Publication2007-119504 or its corresponding European Patent Application PublicationEP 1810963 A1 (Patent Publication 6), and U.S. Pat. No. 4,045,408(Patent Publication 7)).

SUMMARY OF THE INVENTION

The polybenzoxazole resin of Patent Publication 1 has an advantageouseffect of lowering swelling in developing solution, as compared withconventional polyimide resins using a carboxyl group in polyamide acidas a developing solution-soluble group. However, as mentioned above,since there is no phenolic hydroxy group remaining in the final product,it is difficult to make the hydroxy group to contribute to adhesion tosubstrate or the like.

In the cases of Patent Publications 2 and 3, a phenolic hydroxy groupremains in the final product. Therefore, it is possible to improveadhesion to substrate and the like and to use the phenolic hydroxy groupin a cross-linking reaction with epoxy resin. On the other hand, thephenolic hydroxy group remaining in the final product becomes a causefor increasing hygroscopic property. Therefore, in the case of using itfor electronic material components such as LSI, it may cause theincrease of dielectric constant, cracks and the like.

Under such background, Patent Publication 4 proposes the introduction ofa hexafluoroisopropanol moiety (i.e.,2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group) in place ofphenolic hydroxy group. In fact, this publication discloses a synthesisof polyamide or polyimide from a diamine containinghexafluoroisopropanol moiety and a dicarboxylic acid or tetracarboxylicdianhydride. It is mentioned that these polyamide and polyimide showlower dielectric constant and lower water absorption, as compared withconventional polymers derived from a diamine containing a phenolichydroxy group(s).

The polymer of Patent Publication 4 is, however, characterized in thatan aromatic ring is bonded as a side chain to the main chain of thepolymer through an ester bond and that this aromatic ring has ahexafluoroisopropanol moiety as a substituent. Although this polymer hassuperior characteristics, a relatively bulky side chain is bonded to themain chain through a hydrolysable ester bond, and acidic OH groups arepositioned at a terminal portion of the side chain. Therefore,environment for its use is somewhat limited to sufficiently show itscapacities.

Furthermore, the synthesis of a diamine containing ahexafluoroisopropanol moiety as a constituent component of the polymerof Patent Publication 4 requires a relatively high cost. In the case ofa diamine containing a hexafluoroisopropanol moiety, the resin islimited to a resin (e.g., polyamide, polyimide and polybenzoxazole)prepared by the formation of amide bond as a polymerization elementaryreaction, and it cannot be used for synthesizing ester-series resins.

The polymers of Patent Publications 5 and 6 have a polyamide basicskeleton containing a hexafluoroisopropanol moiety as an acidic alcohol,and achieve high transparency, low dielectric constant, low waterabsorption, heat resistance, weather resistance, corrosion resistance,photosensitivity, and low refractive index, which are derived fromfluorine, while maintaining capabilities as heat resistant polymers. Ina final dehydration, ring-closing reaction (a thermal cyclizationbetween a OH group and an amide bond moiety) of the polymers, however,the OH group disappears by incorporation into the resin skeleton.Therefore, it is difficult in the final polymers after the thermalcyclization to sufficiently maintain adhesion and compatibility withother resins, which are derived from OH group.

Furthermore, imine by-products are produced in the productions ofdiamine monomers of Patent Publications 5 and 6, and there occurs a loadof separating the imine by-product from the target polymer.

As an example that a hexafluoroisopropanol moiety has been introducedinto a dicarboxylic acid monomer, Patent Publication 7 discloses aphthalic derivative, which is defined as a dicarboxylic acid derivativecontaining two carboxyl groups at ortho position of the benzene nucleus.In this publication, an anhydride of a phthalic acid derivativecontaining a hexafluoroisopropanol moiety is used as a curing agent forepoxy resins. It is possible to convert this phthalic acid derivative toother compounds by using reactivity of its anhydride. This phthalic acidderivative is, however, not suitable for synthesizing linear polymerssuch as polyester, polyamide and polybenzoxazole.

As mentioned above, there has been a demand for a linear polymer, suchas polyester, polyamide and polybenzoxazole, particularly a novelaromatic polymer oriented to heat resistance, which has a repeating unitderived from a dicarboxylic acid monomer having a hexafluoroisopropanolmoiety.

As a result of an eager examination to meet the above-mentioned demand,the present inventors have reached a novel dicarboxylic acid containingat least one hexafluoroisopropanol moiety in the molecule and novelpolymer compounds obtained by using the same.

That is, we have found a fluorine-containing dicarboxylic acidrepresented by formula (1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring.

We have found that the fluorine-containing dicarboxylic acid hasproperties that are significantly different from those of theabove-mentioned phthalic acid derivative (i.e., a dicarboxylic acidderivative containing two carboxyl groups adjacent to each other on thearomatic ring) of Patent Publication 7. In fact, we have found that thefluorine-containing dicarboxylic acid can perform effectively as a unitfor synthesizing various linear polymers, such as polyester, polyamideand polybenzoxazole.

That is, firstly, we have found a first polymer compound obtained byreacting the fluorine-containing dicarboxylic acid or an ester-formingderivative thereof with a diol represented by formula (2),

HO—R¹—OH   (2)

wherein R¹ represents an organic group that has a valence of at leasttwo and that contains at least one selected from the group consisting ofaliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles,

R¹ may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

a part of hydrogen atoms of R¹ may be replaced with an alkyl group,fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

The first polymer compound is represented by formula (6),

wherein n and R¹ are respectively defined as in formulas (1) and (2),the two —CO groups are not adjacent to each other on the aromatic ring,and m represents a positive integer.

Secondly, we have found a second polymer compound obtained by reactingthe fluorine-containing dicarboxylic acid or an amide-forming derivativethereof with a diamine represented by formula (3),

H₂N—R²—NH₂   (3)

wherein R² represents an organic group that has a valence of at leasttwo and that contains at least one selected from the group consisting ofaliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles,

R² may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

a part of hydrogen atoms of R² may be replaced with an alkyl group,fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

The second polymer compound is represented by formula (7),

wherein n and R² are respectively defined as in formulas (1) and (3),the two —CO groups are not adjacent to each other on the aromatic ring,and m represents a positive integer.

Thirdly, we have found a third polymer compound obtained by reacting thefluorine-containing dicarboxylic acid or an amide-forming derivativethereof with a diaminodiol represented by formula (4),

wherein R³ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles,

R³ may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

a part of hydrogen atoms of R³ may be replaced with an alkyl group,fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

The third polymer compound is represented by formula (8),

wherein n and R³ are respectively defined as in formulas (1) and (4),the two —CO groups are not adjacent to each other on the aromatic ring,and m represents a positive integer.

Fourthly, we have found a fourth polymer compound obtained by reactingthe fluorine-containing dicarboxylic or an amide-forming derivativethereof with a diaminodiol represented by formula (5),

wherein R⁴ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles,

R⁴ may contain fluorine, chlorine, oxygen, sulfur or nitrogen,

a part of hydrogen atoms of R⁴ may be replaced with an alkyl group,fluoroalkyl group, carboxyl group, hydroxy group, or cyano group.

The fourth polymer compound is represented by formula (10),

wherein n and R⁴ are respectively defined as in formulas (1) and (5),the two —CO groups are not adjacent to each other on the aromatic ring,and m represents a positive integer.

Furthermore, we have found a fifth polymer compound obtained by adehydration, ring-closing reaction of the third polymer compoundrepresented by formula (8). The fifth polymer compound is represented byformula (9),

wherein n, R³ and m are respectively defined as in formulas (1), (4) and(8), and a main chain of the polymer compound is not bonded to adjacentpositions on the aromatic ring.

Furthermore, we have found a sixth polymer compound obtained by adehydration, ring-closing reaction of the fourth polymer compoundrepresented by formula (10). The sixth polymer compound is representedby formula (11),

wherein n, R⁴ and m are respectively defined as in formulas (1), (5) and(10), and a main chain of the polymer compound is not bonded to adjacentpositions on the aromatic ring.

The first to sixth polymer compounds according to the present inventionare resins characterized in that fluorine is contained and that a freeacidic OH group(s) exists in the vicinity of the polymer main chain. Dueto the existence of this acidic OH group, the resins show superiorphotosensitivity, adhesion, compatibility with other resins (forexample, showing of a prompt and uniform alkali solubility), orreactivity (for example, reactivity for serving as cross-linkingpoints).

It is a great advantage that the OH group introduction does almost notdamage the first to sixth polymer compounds with respect tocharacteristics derived from fluorine atom, such as low waterabsorption, low dielectric constant, high weather resistance, highcorrosion resistance, transparency and low refractive index. This issupported by the fact that the polymer compounds of the presentinvention show clearly superior values in water absorptioncharacteristics and dielectric constant, as compared with theircorresponding polymer compounds each containing a phenolic hydroxy group(see the after-mentioned Examples and Comparative Examples).

Of the above first to sixth polymer compounds, the fifth and sixthpolymer compounds each obtained by the above dehydration, ring-closingreaction are useful substances, since they are particularly high in heatresistance.

That is, we have succeeded in finding novel polymer compounds eachhaving (a) a heat resistance derived from a basic skeleton of thepolymer, (b) characteristics derived from fluorine atom, such as lowwater absorption, low dielectric constant, high weather resistance, highcorrosion resistance, transparency, and low refractive index, (c)characteristics derived from acidic OH group, such as photosensitivity,adhesion, compatibility, and reactivity, and a good balance of these(a), (b) and (c).

The fluorine-containing dicarboxylic acid represented by formula (1) ofthe present invention contains at least one hexafluoroisopropanol moietyintroduced into dicarboxylic acid. With this, it became possible toavoid the above-mentioned problem of imine by-product production uponintroducing a hexafluoroisopropanol moiety into diamine monomers inPatent Publications 5 and 6.

Furthermore, we have found a simple process for producing5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid, which corresponds to the fluorine-containing dicarboxylic acidrepresented by formula (1). This process (first process) includes thestep of carbonylating5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12),

wherein X represents a halogen that is fluorine, chlorine, bromine oriodine, trifluoromethanesulfonate group, C₁-C₄ alkylsulfonate group, orarylsulfonate group.

The starting material of the first process,5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene,can be produced by a second process including the steps of:

(a) reacting a 1,3,5-trihalobenzene represented by formula (13),

wherein X represents a halogen that is fluorine, chlorine, bromine oriodine, trifluoromethanesulfonate group, C₁-C₄ alkylsulfonate group, orarylsulfonate group,

with an alkylmagnesium halide, metallic magnesium or alkyllithium; and

(b) treating a product of the step (a) with hexafluoroacetone.

DETAILED DESCRIPTION

In the following, the present invention is exemplarily described indetail by certain embodiments. A person skilled in the art may modifythe embodiments without deviating from the gist of the presentinvention. It should be understood that such modification is in thescope of the present invention.

NOVEL FLUORINE-CONTAINING DICARBOXYLIC ACID

As stated above, a novel fluorine-containing dicarboxylic acid accordingto the present invention is represented by formula (1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring.

Specific examples of the fluorine-containing dicarboxylic acid include2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2,4-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2,5-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,4,5-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,4,6-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2,4,5-tris[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2,4,6-tris[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,4,5,6-tris[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2,4,5,6-tetrakis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid,2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid,3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid,2,3-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid,2,5-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid,2,6-bis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid,2,3,5-tris[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid, and2,3,5,6-tetrakis[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid.

The fluorine-containing dicarboxylic acid represented by formula (1) ispreferably one wherein n is 1 or 2 due to its availability, particularlypreferably one wherein n is 1 due to its easy production.

It is an important point of the present invention that a phthalic acidderivative (i.e., a dicarboxylic acid derivative in which two carboxylicgroups are adjacent to each other on the aromatic ring) is excluded fromthe fluorine-containing dicarboxylic acid of the present invention. Inother words, the fluorine-containing dicarboxylic acid represented byformula (1) is a compound in which two carboxylic groups are at meta orpara position. This position of the two carboxylic groups unexpectedlyprovides the fluorine-containing dicarboxylic acid with goodpolymerizability.

The process for synthesizing the fluorine-containing dicarboxylic acidcan be based on Journal of Organic Chemistry, 1965, Volume 30, pp.998-1001 and U.S. Pat. No. 4,045,408. That is, as shown in the followingreaction formula [1], a xylene (o-xylene, m-xylene or p-xylene) isreacted with hexafluoroacetone to introduce one to four2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl groups. Then, themethyl groups are oxidized by using an oxidizer (e.g., potassiumpermanganate) to obtain the target dicarboxylic acid.

wherein n represents an integer of 1-4, and x represents an arbitrarynumber of 0-3.

By using the above process, it is possible to produce2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid and4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid, which are novel dicarboxylic acids (see Examples 1 and 2).

NOVEL POLYMER COMPOUNDS OBTAINED BY USING NOVEL FLUORINE-CONTAININGDICARBOXYLIC ACID

As a use of the fluorine-containing dicarboxylic acid according to thepresent invention, it can be polymerized to produce polymer compounds.Since this fluorine-containing dicarboxylic acid represented by formula(1) has at least one hexafluoroisopropanol moiety(2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group), it has atleast three functional groups at the same time in the molecule. These atleast three functional groups can effectively be used for producingpolymer compounds. Specifically, it is preferable to use reactivity ofdicarboxylic groups.

In formulas (6) to (11) of the polymer compounds of the presentinvention, m (a positive integer) means the number of the repetitions ofthe monomer unit in the polymer compound. It is preferably 5-10,000,more preferably 10-1,000. The polymer compound of the present inventionrefers to a mixture of polymer compounds having a certain range of thedegree of polymerization. It is preferably 1,000-5,000,000, particularlypreferably 2,000-200,000, in weight average molecular weight. It ispossible to set the degree of polymerization and molecular weight of thepolymer compound at desired values by suitably adjusting theafter-mentioned polymerization conditions.

POLYESTER TYPE POLYMER COMPOUND

It is possible to conduct a polymerization by bringing the dicarboxylicacid (a fluorine-containing polymerizable monomer) represented byformula (1) into contact with a diol represented by formula (2),

HO—R¹—OH   (2)

in a given range of temperature, thereby obtaining a polyester typepolymer compound represented by formula (6).

Specific examples of the diol represented by formula (2) includecatechol (1,2-benzenediol), 1,3-benzenediol, 2,2′-dihydroxybiphenyl,4,4′-dihydroxybiphenyl, 2,2′-methylenediphenol, 4,4′-methylenediphenol,ethylene glycol, propylene glycol, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)-3-methylpropane,2,2-bis(4-hydroxyphenyl)butane, 3,3-bis(4-hydroxyphenyl)pentane,2,2-bis(4-hydroxyphenyl)-4-methylpentane,3,3-bis(4-hydroxyphenyl)hexane,2,2-bis(3-chloro-4-hydroxyphenyl)propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,2,2-bis(3-bromo-4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,2,2-bis(3-methyl-4-hydroxyphenyl)propane, and2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

The polyester type polymer compound can be produced by using aconventional polyester production process without particular limitation.For example, the polymer compound represented by formula (6) can beproduced by a direct polycondensation (dehydrocondensation) between thefluorine-containing dicarboxylic acid represented by formula (1) and thediol represented by formula (2) in the presence of a condensing agent.Furthermore, it is also possible to use an ester-forming derivative ofthe fluorine-containing dicarboxylic acid. Herein, “ester-formingderivative” refers to a compound that easily forms an ester bond with achemical reaction. In fact, the fluorine-containing dicarboxylic acidcan be converted into an ester-forming derivative, such as acid halide(e.g., dichloride and dibromide of the dicarboxylic acid), dialkylester(e.g., dimethyl ester and diethyl ester of the dicarboxylic acid), esterhaving an active ester group (e.g., phenylester group, pyridylestergroup, succinimide ester group), and mixed acid anhydride. Then, it ispossible to produce the polymer compound represented by formula (6) byreacting such ester-forming derivative with the diol represented byformula (2). In this case, it is also possible to use a polymerdissolution accelerator (i.e., a metal salt such as lithium bromide andlithium chloride) and a dehydrating agent such as sulfuric acid.

The process and the conditions of polymerization (polycondensation) arenot particularly limited. For example, it is possible to use a firstprocess in which an ester-forming derivative of the fluorine-containingdicarboxylic acid and the diol are dissolved or melted with each otherat a temperature of 150° C. or higher to conduct the reaction withoutsolvent. It is possible to use a second process in which the reaction isconducted in organic solvent at a high temperature (preferably 150° C.or higher). It is possible to use a third process in which the reactionis conducted in organic solvent at a temperature of −20 to 80° C.

It is simplest to use a process by mixing an ester-forming derivative ofthe fluorine-containing dicarboxylic acid represented by formula (1)with the diol represented by formula (2) in organic solvent to conductthe polycondensation. The molar ratio of this ester-forming derivativeto the diol may be 0.5 to 1.5, preferably 0.8 to 1.2. Similar to normalpolycondensation reactions, molecular weight of the obtained polymerbecomes larger as this molar ratio gets closer to 1.

The organic solvent usable in the polycondensation is not particularlylimited, as long as it can dissolve the both reactants. Its examplesinclude amide solvents (e.g., N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide,and N-methyl-2-pyrrolydone), aromatic solvents (e.g., benzene, anisole,diphenyl ether, nitrobenzene, and benzonitrile), halogen-containingsolvents (e.g., chloroform, dichloromethane, 1,2-dichloroethane, and1,1,2,2-tetrachloroethane), and lactones (e.g., γ-butyrolactone,γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, andα-methyl-γ-butyrolactone. It is effective to conduct the reaction undercoexistence of an acid acceptor (e.g., pyridine and triethylamine) withsuch organic solvent. In particular, if the above amide solvent is used,the solvent itself becomes an acid acceptor. With this, it is possibleto obtain a polyester resin that is high in degree of polymerization.

POLYAMIDE TYPE POLYMER COMPOUND

It is possible to conduct a polymerization by bringing the dicarboxylicacid (a fluorine-containing polymerizable monomer) represented byformula (1) into contact with a diamine represented by formula (3),

H₂N—R²—NH₂   (3)

in a given range of temperature, thereby obtaining a polyamide typepolymer compound represented by formula (7).

Specific preferable examples of the diamine represented by formula (3)include 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride,3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl,3,3′-bis(trifluoromethyl)-5,5′-diaminobiphenyl,bis(trifluoromethyl)-4,4′-diaminodiphenyl, bis(fluorinatedalkyl)-4,4′-diaminodiphenyls, dichloro-4,4′-diaminodiphenyl,dibromo-4,4′-diminodiphenyl, bis(fluorinatedalkoxy)-4,4′-diaminodiphenyls, diphenyl-4,4′-diaminodiphenyl,4,4′-bis(4-aminotetrafluorophenoxy)tetrafluorobenzene,4,4′-bis(4-aminotetrafluorophenoxy)octafluorobiphenyl,4,4′-binaphthylamine, o-, m- or p-phenylenediamine, 2,4-diaminotoluene,2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene,dimethyl-4,4′-diaminodiphenyl, dialkyl-4,4′-diaminodiphenyls,dimethoxy-4,4′-diaminodiphenyl, diethoxy-4,4′-diaminodiphenyl,4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether,4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone,4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone,1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl,bis(4-(3-aminophenoxy)phenyl)sulfone,bis(4-(4-aminophenoxy)phenyl)sulfone,2,2-bis(4-(4-aminophenoxy)phenyl)propane,2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane,2,2-bis(4-(3-aminophenoxy)phenyl)propane,2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane,2,2-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)hexafluoropropane,2,2-bis(4-(3-amino-5-trifluoromethylphenoxy)phenyl)hexafluoropropane,2,2-bis(4-aminophenyl)hexafluoropropane,2,2-bis(3-aminophenyl)hexafluoropropane,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,2,2-bis(3-amino-4-methylphenyl)hexafluoropropane,4,4′-bis(4-aminophenoxy)octafluorobiphenyl, and 4,4′-diaminobenzanilide.

The polyamide type polymer compound can be produced by using aconventional polyamide production process without particular limitation.For example, the polymer compound represented by formula (7) can beproduced by a direct polycondensation (dehydrocondensation) between thefluorine-containing dicarboxylic acid represented by formula (1) and thediamine represented by formula (3) in the presence of a condensingagent. Furthermore, it is also possible to use an amide-formingderivative of the fluorine-containing dicarboxylic acid. Herein,“amide-forming derivative” refers to a compound that easily forms anamide bond with a chemical reaction. In fact, the fluorine-containingdicarboxylic acid can be converted into an amide-forming derivative,such as acid halide (e.g., dichloride and dibromide of the dicarboxylicacid), dialkylester (e.g., dimethyl ester and diethyl ester of thedicarboxylic acid), ester having an active ester group (e.g.,phenylester group, pyridylester group, succinimide ester group), andmixed acid anhydride. Then, it is possible to produce the polymercompound represented by formula (7) by reacting such amide-formingderivative with the diamine represented by formula (3). In this case, itis also possible to use a polymer dissolution accelerator (i.e., a metalsalt such as lithium bromide and lithium chloride) and a dehydratingagent such as sulfuric acid.

The process and the conditions of polymerization (polycondensation) arenot particularly limited. For example, it is possible to use a firstprocess in which an amide-forming derivative of the fluorine-containingdicarboxylic acid and the diamine are dissolved or melted with eachother at a temperature of 150° C. or higher to conduct the reactionwithout solvent. It is possible to use a second process in which thereaction is conducted in organic solvent at a high temperature(preferably 150° C. or higher). It is possible to use a third process inwhich the reaction is conducted in organic solvent at a temperature of−20 to 80° C.

It is simplest to use a process by mixing an amide-forming derivative ofthe fluorine-containing dicarboxylic acid represented by formula (1)with the diamine represented by formula (3) in organic solvent toconduct the polycondensation. The molar ratio of this amide-formingderivative to the diamine may be 0.5 to 1.5, preferably 0.8 to 1.2.Similar to normal polycondensation reactions, molecular weight of theobtained polymer becomes larger as this molar ratio gets closer to 1.

The organic solvent usable in the polycondensation is not particularlylimited, as long as it can dissolve the both reactants. Its examplesinclude the same organic solvents as those for producing the polyestertype polymer compound. It is effective to conduct the reaction undercoexistence of an acid acceptor (e.g., pyridine and triethylamine) withsuch organic solvent. In particular, if the above amide solvent is used,the solvent itself becomes an acid acceptor. With this, it is possibleto obtain a polyamide resin that is high in degree of polymerization.

POLYAMIDE DIOL TYPE POLYMER COMPOUND

It is possible to conduct a polymerization by bringing the dicarboxylicacid (a fluorine-containing polymerizable monomer) represented byformula (1) into contact with a diaminodiol represented by formula (4),

in a given range of temperature, thereby obtaining a polyamide diol typepolymer compound represented by formula (8).

Specific examples of the diaminodiol represented by formula (4) include2,4-diamino-1,5-benzenediol, 3,3′-dihydroxy-4,4′-diaminobiphenyl,3,3′-diamino-4,4′-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)ketone,bis(3-amino-4-hydroxyphenyl)sulfide, bis(3-amino-4-hydroxyphenyl)ether,bis(3-hydroxy-4-aminophenyl)sulfone,2,2-bis(3-amino-4-hydroxyphenyl)propane,2,2-bis(3-hydroxy-4-aminophenyl)propane,bis(3-hydroxy-4-aminophenyl)methane,2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane andbis(3-amino-4-hydroxyphenyl)difluoromethane.

The polyamide diol type polymer compound can be produced by using aconventional polyamide diol production process without particularlimitation. For example, the polymer compound represented by formula (8)can be produced by a direct polycondensation (dehydrocondensation)between the fluorine-containing dicarboxylic acid represented by formula(1) and the diaminodiol represented by formula (4) in the presence of acondensing agent. Furthermore, it is also possible to use anamide-forming derivative of the fluorine-containing dicarboxylic acid.In fact, the fluorine-containing dicarboxylic acid can be converted intoan amide-forming derivative, such as acid halide (e.g., dichloride anddibromide of the dicarboxylic acid), dialkylester (e.g., dimethyl esterand diethyl ester of the dicarboxylic acid), ester having an activeester group (e.g., phenylester group, pyridylester group, succinimideester group), and mixed acid anhydride. Then, it is possible to producethe polymer compound represented by formula (8) by reacting suchamide-forming derivative with the diaminodiol represented by formula(4). In this case, it is also possible to use a polymer dissolutionaccelerator (i.e., a metal salt such as lithium bromide and lithiumchloride) and a dehydrating agent such as sulfuric acid.

The process and the conditions of polymerization (polycondensation) arenot particularly limited. They may be the same as those for producingthe polyamide type polymer compound represented by formula (7), sinceelementary reaction of the polymerization is an amide-forming reaction.Furthermore, it is possible to use the same organic solvent as that forproducing the polyamide type polymer compound.

It is possible to subject the polyamide diol type polymer compound to adehydration, ring-closing reaction to convert it into a polybenzoxazoletype polymer compound represented by formula (9).

It is possible to use a conventional dehydration, ring-closing reactionwithout particular limitation. The cyclization can be conducted byvarious methods for accelerating the dehydration condition, such asheat, acid catalyst, and base catalyst. A heating ring-closing can beconducted at a temperature of 80-400° C., particularly preferably150-350° C. If the ring-closing temperature is lower than 150° C., thering closing rate may become too low. This may damage strength of thepolybenzoxazole film. If it is higher than 350° C., the coated film maybecome colored or brittle. The acid catalyst may be selected fromp-toluenesulfonic acid, methanesulfonic acid, etc. The base catalyst maybe selected from triethylamine, pyridine, etc. If the polybenzoxazoleafter the ring closing is soluble in organic solvent, the ring closingcan chemically be conducted by using a dehydration reagent (e.g., aceticanhydride) and an organic base (e.g., pyridine and triethylamine).

It is possible by the cyclization (ring-closing) to conduct a resinmodification accompanied with considerable property changes, such asheat resistance improvement, solubility change, lowering of refractiveindex and dielectric constant, and occurrence of water repellency andoil repellency.

HIGHLY FLUORINATED POLYAMIDE TYPE POLYMER COMPOUND

It is possible to conduct a polymerization by bringing the dicarboxylicacid (a fluorine-containing polymerizable monomer) represented byformula (1) into contact with a diaminodiol represented by formula (5),

in a given range of temperature, thereby obtaining a highly fluorinatedpolyamide type polymer compound represented by formula (10).

Specific examples of the diaminodiol represented by formula (5) havingtwo hexafluoroisopropanol moieties include the following compounds.

The highly fluorinated polyamide type polymer compound can be producedby using a conventional polyamide production process without particularlimitation. For example, the polymer compound represented by formula(10) can be produced by a direct polycondensation (dehydrocondensation)between the fluorine-containing dicarboxylic acid represented by formula(1) and the diaminodiol represented by formula (5) in the presence of acondensing agent. Furthermore, it is also possible to use anamide-forming derivative of the fluorine-containing dicarboxylic acid.In fact, the fluorine-containing dicarboxylic acid can be converted intoan amide-forming derivative, such as acid halide (e.g., dichloride anddibromide of the dicarboxylic acid), dialkylester (e.g., dimethyl esterand diethyl ester of the dicarboxylic acid), ester having an activeester group (e.g., phenylester group, pyridylester group, succinimideester group), and mixed acid anhydride. Then, it is possible to producethe polymer compound represented by formula (10) by reacting suchamide-forming derivative with the diaminodiol represented by formula(5). In this case, it is also possible to use a polymer dissolutionaccelerator (i.e., a metal salt such as lithium bromide and lithiumchloride) and a dehydrating agent such as sulfuric acid.

The process and the conditions of polymerization (polycondensation) arenot particularly limited. They may be the same as those for producingthe polyamide type polymer compound represented by formula (7), sinceelementary reaction of the polymerization is an amide-forming reaction.Furthermore, it is possible to use the same organic solvent as that forproducing the polyamide type polymer compound.

It is possible to subject the highly fluorinated polyamide type polymercompound to a dehydration, ring-closing reaction to convert it into aheterocyclic type polymer compound represented by formula (11)

The conditions for conducting the dehydration, ring-closing reaction arenot particularly limited. The cyclization can be conducted by variousmethods for accelerating the dehydration condition, such as heat, acidcatalyst, and base catalyst. It is possible to achieve the dehydration,ring-closing under a milder condition than that for forming the oxazolering of formula (9).

The heterocyclic polymer compound represented by formula (11) shows alower dielectric constant, a lower water absorption and a highertransparency than the polybenzoxazole represented by formula (9) does,since the former contains hetero rings with trifluoromethyl groups.

It is possible to use the fluorine-containing polymer of the presentinvention in the form of varnish, where it is dissolved in organicsolvent, powder, film, or solid. According to need, it is optional toadd a suitable additive (e.g., oxidation stabilizer, filler, silanecoupling agent, photosensitizing agent, photo polymerization initiator,and sensitizer) to the polymer obtained. In using the polymer in theform of varnish, it can be applied onto a substrate (e.g., glass,silicon wafer, metal, metal oxide, ceramic, and resin) by a normalmethod (e.g., spin coating, spraying, flow coating, impregnationcoating, and brush coating).

PROCESS FOR PRODUCING5-[2,2,2-TRIFLUORO-1-HYDROXY-1-(TRIFLUOROMETHYL)ETHYL]-1,3-BENZENEDICARBOXYLICACID

As stated above, it is possible to obtain4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,2-benzenedicarboxylicacid (see Journal of Organic Chemistry, 1965, Vol. 30, pp. 998-1001;U.S. Pat. No. 4,045,408; and the following reaction formula [2]) by aprocess in which a starting material of o-xylene is reacted withhexafluoroacetone to introduce a2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl group, and then thetwo methyl groups are oxidized by using an oxidizing agent (e.g.,potassium permanganate). Similarly, it is possible to obtain4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid (see Example 1 and the following reaction formula [3]) by replacingo-xylene with m-xylene. Similarly, it is possible to obtain2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid (see Example 2 and the following reaction formula [4]) by replacingo-xylene with p-xylene.

As stated above, however, it is difficult to synthesize linear polymers,such as polyester, polyamide and polybenzoxazole, particularly aromaticpolymers oriented to heat resistance, from4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,2-benzenedicarboxylicacid, which is obtained by Reaction Formula [2] and is not according tothe present invention.

In contrast, each of4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid and2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid, which are respectively obtained by Reaction Formulas [3] and [4]and are according to the present invention, has a higher linearity andthereby suitably functions as a structural unit of various polymers.

From the viewpoint of symmetry, however, it is considered that5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid represented by the following formula,

is a more superior structural unit. The process for producing a compoundhaving such structure has not been known up to now. This compound cannotbe produced by a process in which m-xylene is reacted withhexafluoroacetone (see Reaction Formula [3]), due to the problem oforientation.

As a result of further research, we have found a process for producingthe target5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid by using a trihalobenzene as the starting material by referring toJournal of Organometallic Chemistry, Vol. 215, 1981, pp. 281-291.

This process includes the steps of:

(a) reacting a 1,3,5-trihalobenzene represented by formula (13),

wherein X represents a halogen that is fluorine, chlorine, bromine oriodine, trifluoromethanesulfonate group, C₁-C₄ alkylsulfonate group, orarylsulfonate group,

with an alkylmagnesium halide, metallic magnesium or alkyllithium;

(b) treating a product of the step (a) with hexafluoroacetone, therebyobtaining5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12),

wherein X is defined as above, and

(c) carbonylating the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzeneinto5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid.

The steps (a) and (b) are as shown in the following Scheme [1].

Specific examples of the 1,3,5-trihalobenzene used in the step (a)include 1,3,5-trifluorobenzene, 1,3,5-tricholorobenzene,1,3,5-tribromobenzene, 1,3,5-triiodobenzene,1,3,5-tris(trifluoromethanesulfonyl)benzene,1,3,5-tri(methanesulfonyl)benzene, 1,3,5-tri(benzenesulfonyl)benzene,and 1,3,5-tri(p-tosylsulfonyl)benzene. Of these,1,3,5-tricholorobenzene, 1,3,5-tribromobenzene and 1,3,5-triiodobenzeneare preferable, and 1,3,5-tribromobenzene is particularly preferable.

The step (a) may be conducted by a first reaction in which the1,3,5-trihalobenzene is reacted with an alkylmagnesium haliderepresented by formula (14)

R′ MgZ   (14)

wherein R′ represents an alkyl group, and Z represents a halogen that ischlorine, bromine or iodine. The alkyl group R′ may be straight-chain orbranched and may be a C₁-C₈ alkyl group. Its specific examples includeethyl group, propyl group, isopropyl group, butyl group, isobutyl group,t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, and2-ethylhexyl group. The halogen Z is preferably a chlorine atom orbromine atom.

The first reaction may be conducted in a suitable solvent, preferablyunder an inert gas atmosphere, to obtain 3,5-dihalophenylmagnesiumhalide (see Scheme 1).

The amount of the alkylmagnesium halide by mol may be 0.3 to 5 times,preferably 1 to 2 times, that of the 1,3,5-trihalobenzene represented byformula (13).

In the first reaction, the solvent is preferably an ether seriessolvent. Its specific examples include diethyl ether, diisopropyl ether,t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, anddioxane. The amount of the solvent by volume may be 0.5 to 10 times,preferably 1 to 5 times, that of the 1,3,5-trihalobenzene represented byformula (13). The inert gas is preferably nitrogen gas or argon gas.

The reaction temperature for conducting the first reaction may be in arange of 0° C. to around the reflux temperature of the solvent,preferably 0° C. to 65° C., more preferably 10° C. to 40° C.

The reaction time for conducting the first reaction is not particularlylimited. The optimum reaction time may vary depending on temperature andthe amount of the substrate used. Therefore, it is preferable to conductthe reaction, while monitoring progress of the reaction by ageneral-purpose analytical means, such as gas chromatography, and toterminate the first reaction after confirming that the raw material hassufficiently been consumed.

The alkylmagnesium halide may be a commercial product or one producedupon conducting the first reaction.

The step (a) may be conducted by a second reaction in which the1,3,5-trihalobenzene represented by formula (13) is reacted withmetallic magnesium in a suitable solvent, preferably under an inert gasatmosphere, to obtain 3,5-dihalophenylmagnesium halide (see Scheme 1).

The metallic magnesium may be in any form such as bulky form, tape form,foil form, flake form, shave form, or powder form. From the point ofreactivity, it is preferably flake form, shave form or powder form,particularly preferably powder form. The amount of the metallicmagnesium by mol may be 0.8 to 5 times, preferably 1 to 2 times, that ofthe 1,3,5-trihalobenzene represented by formula (13).

In the second reaction, the solvent is preferably an ether seriessolvent. Its specific examples include diethyl ether, diisopropyl ether,t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, anddioxane. The amount of the solvent by volume may be 0.5 to 10 times,preferably 1 to 5 times, that of the 1,3,5-trihalobenzene represented byformula (13). The inert gas is preferably nitrogen gas or argon gas.

The reaction temperature for conducting the second reaction may be in arange of 0° C. to around the reflux temperature of the solvent,preferably 0° C. to 100° C., more preferably 10° C. to 80° C.

The reaction time for conducting the second reaction is not particularlylimited. The optimum reaction time may vary depending on temperature andthe amount of the substrate used. Therefore, it is preferable to conductthe reaction, while monitoring progress of the reaction by ageneral-purpose analytical means, such as gas chromatography, and toterminate the second reaction after confirming that the raw material hassufficiently been consumed.

The step (a) may be conducted by a third reaction in which the1,3,5-trihalobenzene is reacted with an alkyllithium represented byformula (15),

TLi   (15)

where T represents an alkyl group. This alkyl group may bestraight-chain or branched and may be a C₁-C₆ alkyl group. Its specificexamples include methyl group, ethyl group, propyl group, isopropylgroup, butyl group, isobutyl group, t-butyl group, pentyl group, andhexyl group.

The third reaction may be conducted in a suitable solvent, preferablyunder an inert gas atmosphere, to obtain 3,5-dihalophenyllithium (seeScheme 1).

The amount of the alkyllithium by equivalent may be 0.8 to 1.5 times,preferably 1 to 1.2 times, that of the 1,3,5-trihalobenzene representedby formula (13).

In the third reaction, specific examples of the solvent include ethers(e.g., diethyl ether, tetrahydrofuran, dioxane, butyl methyl ether,diisopropyl ether, and ethylene glycol dimethyl ether), alkanes (e.g.,n-pentane, n-hexane, n-heptane, and n-octane), and aromatics (e.g.,benzene, toluene, and xylene).

These solvents may be used singly or in a mixture of at least two. Theamount of the solvent by volume may be 0.5 to 10 times, preferably 1 to5 times, that of the 1,3,5-trihalobenzene represented by formula (13).The inert gas is preferably nitrogen gas or argon gas.

The reaction temperature for conducting the third reaction may be −150°C. to 200° C., preferably −110° C. to around the reflux temperature ofthe solvent.

The reaction time for conducting the third reaction is not particularlylimited. The optimum reaction time may vary depending on temperature andthe amount of the substrate used. Therefore, it is preferable to conductthe reaction, while monitoring progress of the reaction by ageneral-purpose analytical means, such as gas chromatography, and toterminate the third reaction after confirming that the raw material hassufficiently been consumed.

The alkyllithium may be a commercial product or one produced uponconducting the third reaction.

The step (b) is conducted by reacting an intermediate obtained by thestep (a) with hexafluoroacetone (see Scheme 1).

The intermediate obtained by each of the first to third reactions of thestep (a) is a highly reactive, unstable substance. Therefore, it isnormal to subject the reaction liquid after the step (a) to the step (b)without conducting a purification to isolate the intermediate.

In the step (b), hexafluoroacetone (boiling point: −28° C.) may bebubbled as gas into the reaction liquid or may be added as liquid bycooling. It is, however, necessary to use a hexafluoroacetone that issufficiently dry and contains no water. Its hydrate is of no use.

In the case of using hexafluoroacetone as gas, it is preferable to usean apparatus (a cooling apparatus or sealed reactor) for preventing leakof hexafluoroacetone. The apparatus is particularly preferably a sealedreactor.

The step (b) may be conducted at a temperature of −200° C. to 50° C.,preferably −150° C. to room temperature, particularly preferably −100°C. to room temperature. If it is lower than −200° C., it may bedifficult to conduct the reaction. If it is higher than 50° C., sidereactions may occur.

It is preferable to conduct the step (b) by using solvent. The solventto be used is not particularly limited, as long as it is not involved inthe reaction. As stated above, it is possible to easily conduct the step(b) by adding hexafluoroacetone to the reaction liquid after the step(a). Therefore, it is preferable to use the solvent itself used in thestep (a).

The reaction time for conducting the step (b) is not particularlylimited. The optimum reaction time may vary depending on temperature andthe amount of the substrate used. Therefore, it is preferable to conductthe reaction, while monitoring progress of the reaction by ageneral-purpose analytical means, such as gas chromatography, and toterminate the reaction after confirming that the raw material hassufficiently been consumed.

After the step (b), it is possible to obtain5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12) by a normal means such as extraction,distillation or crystallization. According to need, it can be purifiedby column chromatography, recrystallization, etc.

The step (c) is conducted by carbonylating5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene,which is represented by formula (12), into5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid. This carbonylation may be conducted as shown in Scheme 2.

As shown in Scheme 2, the step (c) may be conducted by two steps of (d)and (e).

The step (d) may be conducted by a first reaction in which5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzene,which is represented by formula (12), is reacted with an alkylmagnesiumhalide represented by formula (14)

R′ MgZ   (14)

wherein R′ represents an alkyl group, and Z represents a halogen that ischlorine, bromine or iodine. The alkyl group R′ may be straight-chain orbranched and may be a C₁-C₈ alkyl group. Its specific examples includeethyl group, propyl group, isopropyl group, butyl group, isobutyl group,t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, and2-ethylhexyl group. The halogen Z is preferably a chlorine atom orbromine atom.

The first reaction may be conducted in a suitable solvent, preferablyunder an inert gas atmosphere, to obtain a Grignard reagent (see Scheme2).

The amount of the alkylmagnesium halide by mol may be 1 to 10 times,preferably 2 to 4 times, that of the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12).

In the first reaction, the solvent is preferably an ether seriessolvent. Its specific examples include diethyl ether, diisopropyl ether,t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, anddioxane. The amount of the solvent by volume may be 0.5 to 10 times,preferably 1 to 5 times, that of the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12). The inert gas is preferably nitrogen gas orargon gas.

The reaction temperature for conducting the first reaction may be in arange of 0° C. to around the reflux temperature of the solvent,preferably 0° C. to 65° C., more preferably 10° C. to 40° C. Thereaction time may be 1 to 48 hours. The alkylmagnesium halide may be acommercial product or one produced upon conducting the first reaction.

The step (d) may be conducted by a second reaction in which the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12) is reacted with metallic magnesium in asuitable solvent, preferably under an inert gas atmosphere, to obtain aGrignard reagent (see Scheme 2).

The metallic magnesium may be in any form such as bulky form, tape form,foil form, flake form, shave form, or powder form. From the point ofreactivity, it is preferably flake form, shave form or powder form,particularly preferably powder form. The amount of the metallicmagnesium by mol may be 1 to 10 times, preferably 2 to 5 times, that ofthe5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12).

In the second reaction, the solvent is preferably an ether seriessolvent. Its specific examples include diethyl ether, diisopropyl ether,t-butoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, anddioxane. The amount of the solvent by volume may be 0.5 to 10 times,preferably 1 to 5 times, that of the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12). The inert gas is preferably nitrogen gas orargon gas.

The reaction temperature for conducting the second reaction may be in arange of 0° C. to around the reflux temperature of the solvent,preferably 0° C. to 100° C., more preferably 10° C. to 80° C. Thereaction time may be 1 to 48 hours.

The step (d) may be conducted by a third reaction in which the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12) is reacted with an alkyllithium representedby formula (15),

TLi   (15)

where T represents an alkyl group. This alkyl group may bestraight-chain or branched and may be a C₁-C₆ alkyl group. Its specificexamples include methyl group, ethyl group, propyl group, isopropylgroup, butyl group, isobutyl group, t-butyl group, pentyl group, andhexyl group.

The third reaction may be conducted in a suitable solvent, preferablyunder an inert gas atmosphere, to obtain an organic lithium reagent (seeScheme 2).

The amount of the alkyllithium by equivalent may be 1 to 10 times,preferably 2 to 5 times, that of the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12).

In the third reaction, specific examples of the solvent include ethers(e.g., diethyl ether, tetrahydrofuran, dioxane, butyl methyl ether,diisopropyl ether, and ethylene glycol dimethyl ether), alkanes (e.g.,n-pentane, n-hexane, n-heptane, and n-octane), and aromatics (e.g.,benzene, toluene, and xylene).

These solvents may be used singly or in a mixture of at least two. Theamount of the solvent by volume may be 0.5 to 10 times, preferably 1 to5 times, that of the5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12). The inert gas is preferably nitrogen gas orargon gas.

The reaction temperature for conducting the third reaction may be −150°C. to 200° C., preferably −110° C. to around the reflux temperature ofthe solvent. The reaction time may be 1 to 48 hours. The alkyllithiummay be a commercial product or one produced upon conducting the thirdreaction.

The step (e) is a carbonylation of an intermediate (i.e., the Grignardreagent or organic lithium reagent) obtained by the step (d) into thetarget5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid by carbon dioxide as a carbonylation agent (see Scheme 2).

In the step (e), the form of carbon dioxide under ordinary temperatureand ordinary pressure is not particularly limited, and it may take a gasor solid form. A skilled person in the art can select a suitable form.

In the case of replacing the atmosphere of the reaction system withcarbon dioxide in the form of gas, the reaction can be conducted under apressurized condition. In this case, a reactor is charged with thereaction liquid obtained by the step (e), followed by tightly closingthe reactor.

In the case of using carbon dioxide (dry ice) in the form of solid, thereaction can be conducted under ordinary pressure due to its easyhandling.

The carbonylation is conducted by heating with or without stirring. Inthe case of conducting the reaction under pressurized condition, thepressure may be 0.1 to 1.2 kPa, preferably 0.5 to 1.0 kPa, morepreferably 0.5 to 0.8 kPa. If it is lower than 0.1 kPa, the reaction maynot proceed sufficiently, thereby causing low yield or necessity of along time to complete the reaction due to low reaction rate. Even if itis higher than 1.2 kPa, there occurs almost no change in reaction rateand yield of the target product in the carbonylation. Therefore, it isnot preferable.

As the reactor for conducting the reaction under pressurized condition,it is possible to use a metal container such as stainless steel,Hastelloy and Monel metal. In the case of conducting the reaction underordinary pressure, a skilled person in the art can suitably select thereactor.

The reaction temperature upon adding carbon dioxide in the form of gasor solid (dry ice) may be −150° C. to 200° C., preferably −110° C. toaround the reflux temperature of the solvent used.

As an alternative to the two steps (d) and (e), the step (c) may beconducted by one step in which5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12) is reacted with carbon monoxide as acarbonylation agent in the presence of a palladium catalyst and a basicsubstance (see Scheme 2). This reaction is described in detail in thefollowing.

Specific preferable examples of the palladium catalyst includepalladium-carried activated carbon, palladium chloride, palladiumacetate, tetrakis(triphenylphosphine)palladium,bis(dibenzylideneacetonato)palladium, PdCl₂[P(o-Me-Ph)₃]₂,PdCl₂[P(m-Me-Ph)₃]₂, PdCl₂[P(p-Me-Ph)₃]₂, PdCl₂[(PMe)₃]₂,PdBr₂[(PPh)₃]₂, PdCl₂[P(Ph)₂CH₂CH₂P(Ph)₂],PdCl₂[P(Ph)₂CH₂CH₂CH₂CH₂P(Ph)₂], PdCl₂(PhCN)₂, Pd(CO)(PPh₃)₃,PhPdI(PPh₃)₂, PhPdBr(PPh₃)₂, PhPdBr(PMePh₂)₂, PhCl₂(PMePh₂)₂,PhCl₂(PEt₂Ph)₂, PhCl₂(PMe₂Ph)₂, Pd₂Br₄(PPh₃)₂, and PdCl₂[P(Ph)₃]₂, wherePh represents a phenyl group, Me a methyl group, Et an ethyl group,o—ortho substitution, m—meta substitution, and p—para substitution.

Each of these palladium catalysts shows a satisfactory catalyticactivity. It is economically particularly preferable to use a bivalentpalladium complex, such as palladium chloride, palladium acetate,PdCl₂[P(Ph)₃]₂, and PdCl₂[P(Ph)₂CH₂CH₂CH₂CH₂P(Ph)₂], which have lowprices and are easy in handling.

The amount of the palladium catalyst may be 0.00001 to 0.2 moles,preferably 0.001 to 0.1 moles, more preferably 0.001 to 0.05 moles, permol of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12).

It is particularly preferable to use a trivalent phosphorus compound asa promoter to maintain activity of the palladium catalyst. Herein, thepromoter refers to a substance that is added in a small amount toincrease activity or selectivity of the catalyst.

A preferable compound as the promoter is represented by formula (16),

R⁵—(R⁶—)P—R⁷   (16)

wherein R⁵, R⁶ and R⁷ represent the same or different alkyl groups, arylgroups, alkoxy groups, aryloxy groups, or halogen atoms. Its specificexamples include tri-n-butylphosphine, triethylphosphine,triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine,tri-p-tolylphosphine, tri-o-tolylphosphite, and phosphorus trichloride.

Another preferable compound as the promoter is a phosphine representedby formula (17),

(R⁵)₂P-Q-P(R⁶)₂   (17)

wherein R⁵ and R⁶ are defined as in formula (16), and Q represents analkylene group —(CH₂)_(m)— where m represents an integer of 1-8,preferably 1-4. Specific examples of this phosphine include1,1′-bis(diphenylphosphino)ferrocene, 1,4-bis(diphenylphosphino)butane,1,3-bis(diphenylphosphino)propane, 1,2-bis(diphenylphosphinoethane.

The amount of the trivalent phosphorus compound may be 0.5 to 50 molesper mol of the palladium catalyst. Herein, the trivalent phosphoruscompound may be in a first form that is a free compound by itself or ina second form (e.g., PdCl₂[P(Ph)₃]₂) in which it has already beenincorporated as a ligand into a palladium catalyst. It is optional touse the first and second forms at the same time.

The basic substance used in the step (c) is not particularly limited,but it is preferably a basic substance such that pH becomes 8 orgreater. Its specific examples include inorganic bases (e.g., ammonia,sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassiumcarbonate, potassium hydrogencarbonate, and potassium hydroxide), andorganic bases such as tertiary amines (e.g., trimethylamine,triethylamine, tripropylamine, and tributylamine), secondary amines(e.g., diethylamine and dipropylamine), and primary amines (e.g.,propylamine and butylamine). Of these, a preferable one is an organicamine that is a base having a middle strength. Its specific examplesinclude methylamine, ethylamine, isopropylamine, n-butylamine,dimethylamine, diethylamine, triethylamine, di-isopropylethylamine,di-n-butylamine, tri-n-butylamine, tetramethylethylenediamine,N,N-dimethylaniline, N,N-diethylaniline, pyridine, lutidine,2-methylpyridine, N-methylmorpholine, pyperidine, pyrrolydine,morpholine, dibutylamine, and diisopropylamine. Of these, triethylamineis particularly preferable.

The amount of the basic substance may be 1-50 moles, preferably 1-20moles, more preferably 1-10 moles, per mol of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12). The reaction is conducted normally in aninert gas such as nitrogen or argon. In general, the reactiontemperature may be −50° C. to 160° C., preferably −10° C. to 100° C.,more preferably −5° C. to 50° C.

The step (c) as one step is conducted preferably in the presence ofsolvent. The solvent is not particularly limited as long as it is notinvolved in the reaction. Its specific examples include aromatics (e.g.,n-pentane, n-hexane, n-heptane, and n-octane), ethers (e.g., diethylether, tetrahydrofuran, and dioxane), halogenated hydrocarbons (e.g.,dichloromethane and chloroform), alkylketones (e.g., acetone), alcohols(e.g., methanol, ethanol, ethylene glycol, diethylene glycol, andglycerol), aprotic polar solvents (e.g., acetonitrile,N,N-dimethylformamide (DMF), dimethylsufoxide (DMSO), andhexamethylphosphoric triamide (HMPA)) and water. Of these, preferableones are ethers (e.g., diethyl ether, tetrahydrofuran, and dioxane) andalcohols (e.g., methanol, ethanol, ethylene glycol, diethylene glycol,and glycerol). A particularly preferable one is water. These solventsmay be used singly or in combination of at least two. The amount of thesolvent by volume may be 0.5 to 10 times, preferably 1 to 7 times, thatof5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12).

The reaction temperature of the step (c) as one step is not particularlylimited. It may be −50° C. to 200° C., preferably −10° C. to 180° C.,more preferably −5° C. to 150° C.

As stated above, carbon monoxide is used as a carbonylation agent. Thereaction can be conducted under pressurized condition in the case ofreplacing atmosphere of the reaction system with carbon monoxide. Thereaction is conducted by firstly charging the reactor with5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dihalobenzenerepresented by formula (12), palladium catalyst, basic substance andsolvent and then tightly closing the reactor.

The carbonylation is conducted by heating with or without stirring. Inthe case of conducting the reaction under pressurized condition, thepressure may be 0.1 to 1.2 kPa, preferably 0.5 to 1.0 kPa, morepreferably 0.5 to 0.8 kPa. If it is lower than 0.1 kPa, the reaction maynot proceed sufficiently, thereby causing low yield or necessity of along time to complete the reaction due to low reaction rate. Even if itis higher than 1.2 kPa, there occurs almost no change in reaction rateand yield of the target product in the carbonylation. Therefore, it isnot preferable.

As the reactor for conducting the reaction under pressurized condition,it is possible to use a metal container such as stainless steel,Hastelloy and Monel metal.

The post treatment after the reaction of the step (c) by theabove-described two steps (d) and (e) or by the above-described one step(c) may be conducted by a normal post treatment of organic syntheses.For example, it is possible to conduct the post treatment by adding thereaction liquid to a hydrochloric acid aqueous solution, followed byextraction with an organic solvent (e.g., ethyl acetate, toluene, andmethylene chloride), then removing water from the organic layer withdehydrator or the like, and then distilling the solvent off, therebyobtaining a crude product of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid.

It is possible to conduct a further post treatment as a particularlypreferable embodiment by adding an inorganic base (e.g., sodiumhydroxide) aqueous solution to the above crude product to dissolve it asa benzoate in the aqueous solution, followed by extracting organicimpurities with an organic solvent (e.g., hexane and heptane), thenmaking the remaining aqueous solution acidic by using an acid (e.g.,hydrochloric acid), then extraction with an organic solvent (e.g., ethylacetate, toluene, and methylene chloride), then removing water withdehydrator or the like, and then distilling the solvent off, therebyobtaining a purified product of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid.

The following nonlimitative examples are illustrative of the presentinvention.

EXAMPLE 1 PRODUCTION OF4-[2,2,2-TRIFLUORO-1-HYDROXY-1-(TRIFLUOROMETHYL)ETHYL]-1,3-BENZENEDICARBOXYLICACID (DICARBOXYLIC ACID 1)

A 1 L reactor was charged under nitrogen with 100.0 g (0.94 mol) ofm-xylene and 6.3 g (0.047 mol/0.05 eq) of aluminum chloride, followed byadjusting the inside temperature to 10° C. Then, 164.2 g (0.99 mol/1.05eq) of hexafluoroacetone was introduced in a temperature range of 10-25°C. After the introduction, stirring was conducted at room temperaturefor 1 hr. Then, 100 mL of 10% hydrochloric acid was added. The resultingaqueous layer was extracted two times with 40 mL of chloroform. Theresulting organic layers were combined together, followed by removingwater with anhydrous magnesium sulfate, filtration, concentration, andvacuum distillation, thereby obtaining 227.6 g of4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzenerepresented by the following formula. Upon this, purity was 95%, andyield was 84%.

The properties of the obtained4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzenewere as follows.

¹H NMR (DMSO-d₆): δ 8.37 (s, 1H), 7.34 (d, J=8.0 Hz, 1H), 7.12-7.06 (m,2H), 2.52 (s, 3H), 2.26 (s, 3H).

¹⁹F NMR (DMSO-d₆): δ−72.1 (s, 6F, CF₃).

A 300 mL reactor was charged with 10.0 g (36.7 mmol) of the obtained4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-dimethylbenzene(purity: 95%) and 150 mL of 0.15N NaOH, followed by heating to 85° C.Then, 26.1 g (165.3 mmol/4.7 eq) of potassium permanganate was graduallyadded by spending 1 hr, followed by stirring at 90° C. for 4 hr. Afterthe reaction, 11 mL of concentrated hydrochloric acid was added,followed by discoloring with sodium sulfite and extraction with 200 mLof diisopropyl ether. Furthermore, the aqueous layer was extracted twotimes with 50 mL of diisopropyl ether. The combined organic layer wasdehydrated with anhydrous magnesium sulfate, followed by filtration,concentration and drying, thereby obtaining a pale yellow powder. To theobtained pale yellow powder 30 mL of toluene and 4 mL of acetonitrilewere added, followed by reflux and cooling to conduct recrystallization,thereby obtaining 6.1 g of the target4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid represented by the following formula. Upon this, yield was 50%, andpurity was 99.5%.

The properties of the obtained4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid were as follows.

¹H NMR (DMSO-d₆): δ 8.64 (dd, J=8.0 and 1.2 Hz, 1H), 8.61 (s, 1H), 8.28(d, J=8.0 Hz, 1H).

¹³C NMR (DMSO-d₆): δ 165.83 (s), 165.34 (s), 139.80 (s), 138.45 (s),137.56 (s), 128.62 (s), 125.90 (s), 125.77 (s), 121.15 (q, J=284.7 Hz),81.67 (sept, J=32.9 Hz).

¹⁹F NMR (DMSO-d₆): δ −73.7 (s, 6F, CF₃).

EXAMPLE 2 PRODUCTION OF2-[2,2,2-TRIFLUORO-1-HYDROXY-1-(TRIFLUOROMETHYL)ETHYL]-1,4-BENZENEDICARBOXYLICACID (DICARBOXYLIC ACID 2)

A 1 L reactor was charged under nitrogen with 200.0 g (1.88 mol) ofp-xylene and 12.5 g (0.094 mol/0.05 eq) of aluminum chloride, followedby adjusting the inside temperature to 18° C. Then, 327.7 g (1.97mol/1.05 eq) of hexafluoroacetone was introduced in a temperature rangeof 18-25° C. After the introduction, stirring was conducted at roomtemperature for 3 hr. Then, 200 mL of 10% hydrochloric acid was added.The resulting aqueous layer was extracted two times with 50 mL ofchloroform. The resulting organic layers were combined together,followed by removing water with anhydrous magnesium sulfate, filtration,concentration, and vacuum distillation, thereby obtaining 451.3 g of2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzenerepresented by the following formula. Upon this, purity was 92%, andyield was 81%.

The properties of the obtained2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzenewere as follows.

¹H NMR (DMSO-d₆): δ 8.40 (s, 1H), 7.24 (s, 1H), 7.15 (s, 2H), 2.49 (s,3H), 2.26 (s, 3H).

¹⁹F NMR (DMSO-d₆): δ −71.9 (s, 6F, CF₃).

A 5 L reactor was charged with 200.0 g (0.676 mol) of the obtained2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-dimethylbenzene(purity: 92%) and 3.0 L of 0.15N NaOH, followed by heating to 85° C.Then, 480.7 g (3.04 mol/4.5 eq) of potassium permanganate was graduallyadded by spending 3 hr, followed by stirring at 90° C. for 4 hr. Afterthe reaction, 200 mL of concentrated hydrochloric acid was added,followed by discoloring with sodium sulfite and extraction with 1.4 L ofdiisopropyl ether. Furthermore, the aqueous layer was extracted twotimes with 500 mL of diisopropyl ether. The combined organic layer wasdehydrated with anhydrous magnesium sulfate, followed by filtration,concentration and drying, thereby obtaining a pale yellow powder. To theobtained pale yellow powder 560 mL of toluene and 80 mL of acetonitrilewere added, followed by reflux and cooling to conduct recrystallization,thereby obtaining 131.1 g of the target2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid represented by the following formula. Upon this, yield was 58%, andpurity was 99.8%.

The properties of the obtained2-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,4-benzenedicarboxylicacid were as follows.

¹H NMR (DMSO-d₆): δ 8.45 (d, J=7.6 Hz, 1H), 8.31 (d, J=7.6 Hz, 1H), 8.27(s, 1H).

¹³C NMR (DMSO-d₆): δ 165.16 (s), 164.62 (s), 138.93 (s), 136.24 (s),135.2-134.5 (m), 128.8-127.9 (m), 127.56 (s), 124.9-123.8 (m), 120.48(q, J=284.7 Hz), 80.89 (sept, J=33.0 Hz).

¹⁹F NMR (DMSO-d₆): δ −73.8 (s, 6F, CF₃).

EXAMPLE 3 PRODUCTION OF5-[2,2,2-TRIFLUORO-1-HYDROXY-1-(TRIFLUOROMETHYL)ETHYL]-1,3-BENZENEDICARBOXYLICACID (DICARBOXYLIC ACID 3)

Under nitrogen atmosphere, a 500 mL glass flask was charged with 30.0 g(95.0 mmol) of 1,3,5-tribromobenzene and 400 mL of diethyl ether,followed by cooling to −78° C. At −78° C., 60 mL of a 1.6M solutioncontaining 96.0 mmol of n-butyllithium in hexane was added dropwise byspending 1 hr, followed by aging at −78° C. for 1 hr. After confirminglithiation by gas chromatography, 16.6 g (100.0 mmol) ofhexafluoroacetone was bubbled at −78° C., followed by stirring for 1 hr.After stirring, the reaction liquid was added to 400 mL of 2Nhydrochloric acid to separate it into an organic layer and an aqueouslayer. The aqueous layer was extracted with 100 mL of isopropyl ether.The combined organic layer was dried with anhydrous magnesium sulfate,followed by concentration with an evaporator and then soliddistillation, thereby obtaining 23.0 g of1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzene(yield: 60%) represented by the following formula.

The properties of1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzenewere as follows.

¹H NMR (CDCl₃): δ 7.79 (S, 3H).

¹⁹F NMR (CDCl₃): δ −76.0 (S, 6F, CF₃).

A 10 mL autoclave was charged with 1.00 g (2.6 mmol) of the obtained1-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-3,5-dibromobenzene,0.056 g (0.25 mmol) of palladium acetate, 0.263 g (1.0 mmol) oftriphenylphosphine, 1.01 g (10.0 mmol) of triethylamine, 0.50 g ofwater, and 2.0 g of tetrahydrofuran. Then, the reaction was conducted at100° C. for 17 hr under a carbon monoxide pressure of 2 MPa. After thereaction, 5 mL of 2N hydrochloric acid was added to the reaction liquid,followed by extraction with 5 mL of isopropyl ether to separate anorganic layer. To this organic layer 6 mL of 7% sodium hydroxide aqueoussolution was added to separate an aqueous layer. This aqueous layer waswashed with 3 mL of heptane, followed by adding 6 mL of 6N hydrochloricacid. The precipitated solid was isolated by filtration and then washedwith 5 mL of heptane, thereby obtaining 0.35 g of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid (yield: 41%) represented by the following formula.

The properties of5-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-1,3-benzenedicarboxylicacid were as follows.

¹H NMR (CDCl₃): δ 9.27 (S, 1H), 8.58 (t, 1H), 8.46 (s, 2H).

¹⁹F NMR (CDCl₃): δ −73.5 (S, 6F, CF₃).

EXAMPLE 4 SYNTHESIS OF POLYMER 1

A three-necked flask was charged with 2.00 g (6.0 mmol) of DicarboxylicAcid 2, 1.37 g (6.0 mmol) of bisphenol A, 4.19 g (12.6 mmol) oftriphenylphosphine dichloride as a condensing agent, and 12.0 g ofN-methyl-2-pyrrolidone (NMP), followed by stirring at room temperaturefor 3 hr under nitrogen atmosphere. The obtained viscous solution wasadded to 30 mL of methanol. The obtained precipitate was separated byfiltration, followed by vacuum drying at 80° C., thereby obtaining 2.84g of Polymer 1 (yield: 91%). The result is shown in Table 1.

1.00 g of the obtained Polymer 1 and 4.00 g of N,N-dimethylformamide(DMF) were mixed together to prepare a homogeneous solution. Thissolution was filtered, and the filtrate was applied onto a glasssubstrate by spin coating, followed by heating under nitrogen atmosphereat 80° C. for 30 min, at 150° C. for 30 min, and at 250° C. for 1 hr,thereby obtaining a transparent film. After the film was separated fromthe glass substrate, the film maintained its shape. The properties ofthe film are shown in Table 2.

EXAMPLE 5 SYNTHESIS OF POLYMER 2

A three-necked flask was charged with 2.00 g (6.0 mmol) of DicarboxylicAcid 1, 1.37 g (6.0 mmol) of Diamine 1 represented by the followingformula,

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensingagent, and 19.0 g of N-methyl-2-pyrrolidone (NMP), followed by the samesteps as those of Example 4, thereby obtaining Polymer 2 (yield: 90%).The result is shown in Table 1.

1.00 g of the obtained Polymer 2 and 4.00 g of N,N-dimethylformamide(DMF) were mixed together to prepare a homogeneous solution. Thissolution was filtered, and the filtrate was applied onto a glasssubstrate by spin coating, followed by heating under nitrogen atmosphereat 80° C. for 30 min, at 150° C. for 30 min, and at 250° C. for 1 hr,thereby obtaining a transparent film. After the film was separated fromthe glass substrate, the film maintained its shape. The properties ofthe film are shown in Table 2.

EXAMPLE 6 SYNTHESIS OF POLYMER 3

A three-necked flask was charged with 2.00 g (6.0 mmol) of DicarboxylicAcid 3, 2.20 g (6.0 mmol) of Bisaminophenol 1 represented by thefollowing formula,

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensingagent, and 20.0 g of N-methyl-2-pyrrolidone (NMP), followed by the samesteps as those of Example 4, thereby obtaining Polymer 3 (yield: 85%).The result is shown in Table 1.

EXAMPLE 7 SYNTHESIS OF POLYMER 4

1.00 g of Polymer 3 obtained by Example 3 and 4.00 g ofN,N-dimethylformamide (DMF) were mixed together to prepare a homogeneoussolution. This solution was filtered, and the filtrate was applied ontoa glass substrate by spin coating, followed by heating under nitrogenatmosphere at 80° C. for 30 min, at 150° C. for 30 min, at 250° C. for30 min, and at 320° C. for 1 hr, thereby obtaining a transparent film.After the film was separated from the glass substrate, the filmmaintained its shape. The film was found to have a structure of Polymer4 by IR analysis. The properties of the film are shown in Table 2.

EXAMPLE 8 SYNTHESIS OF POLYMER 5

A three-necked flask was charged with 2.00 g (6.0 mmol) of DicarboxylicAcid 3, 3.19 g (6.0 mmol) of Diaminodiol 1 represented by the followingformula,

4.19 g (12.6 mmol) of triphenylphosphine dichloride as a condensingagent, and 26.0 g of N-methyl-2-pyrrolidone (NMP), followed by the samesteps as those of Example 4, thereby obtaining Polymer 5 (yield: 87%).The result is shown in Table 1.

EXAMPLE 9 SYNTHESIS OF POLYMER 6

1.00 g of Polymer 5 obtained by Example 8 and 4.00 g of DMF were mixedtogether to prepare a homogeneous solution. This solution was filtered,and the filtrate was applied onto a glass substrate by spin coating,followed by heating under nitrogen atmosphere at 80° C. for 30 min, at150° C. for 30 min, and at 250° C. for 1 hr, thereby obtaining atransparent film. After the film was separated from the glass substrate,the film maintained its shape. The film was found to have a structure ofPolymer 6 by IR analysis. The properties of the film are shown in Table2.

COMPARATIVE EXAMPLE 1 SYNTHESIS OF POLYMER 7

Example 4 was repeated except in that Dicarboxylic Acid 2 was replacedwith Dicarboxylic Acid 4 represented by the following formula.

With this, a transparent film was obtained. After the film was separatedfrom the glass substrate, the film maintained its shape. The propertiesof the film are shown in Table 2.

COMPARATIVE EXAMPLE 2 SYNTHESIS OF POLYMER 8

Example 5 was repeated except in that Dicarboxylic Acid 1 was replacedwith Dicarboxylic Acid 4 of Comparative Example 1. With this, atransparent film was obtained. After the film was separated from theglass substrate, the film maintained its shape. The properties of thefilm are shown in Table 2.

COMPARATIVE EXAMPLE 3 SYNTHESIS OF POLYMER 9

Example 6 was repeated except in that Dicarboxylic Acid 3 was replacedwith Dicarboxylic Acid 4 of Comparative Example 1. The resulting polymerwas subjected to the same procedures as those of Example 7, therebyobtaining a transparent film having a structure of Polymer 9. After thefilm was separated from the glass substrate, the film maintained itsshape. The properties of the film are shown in Table 2.

COMPARATIVE EXAMPLE 4 SYNTHESIS OF POLYMER 10

Example 8 was repeated except in that Dicarboxylic Acid 3 was replacedwith Dicarboxylic Acid 4 of Comparative Example 1. The resulting polymerwas subjected to the same procedures as those of Example 9, therebyobtaining a transparent film having a structure of Polymer 10. After thefilm was separated from the glass substrate, the film maintained itsshape. The properties of the film are shown in Table 2.

TABLE 1 Polymer No. Mw (Mw/Mn) Example 4 1 25,000 (2.34) Example 5 231,000 (2.52) Example 6 3 37,000 (2.17) Example 8 5 32,000 (2.45)

TABLE 2 Dielectric Water Absorption Polymer No. Constant (%) Example 4 13.10 2.00 Example 5 2 3.40 3.30 Example 7 4 2.70 2.60 Example 9 6 2.502.42 Com. Ex. 1 7 3.40 2.40 Com. Ex. 2 8 3.60 4.00 Com. Ex. 3 9 3.203.20 Com. Ex. 4 10 3.00 3.05

It is understood from Table 2 that Polymers 1, 2, 4 and 6 according toExamples 4, 5, 7 and 9, each polymer having a hexafluoroisopropanolgroup, are respectively lower in dielectric constant and waterabsorption than Polymers 7 to 10 according to Comparative Examples 1 to4, each polymer having a phenolic hydroxy group, in contrast with thehexafluoroisopropanol group.

The entire contents of Japanese Patent Application No. 2007-185257(filed Jul. 17, 2007), of which priority is claimed in the presentapplication, are incorporated herein by reference.

1. A polymer compound obtained by reacting a fluorine-containingdicarboxylic acid represented by formula (1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent each other on the aromatic ring, or an ester-formingderivative of the fluorine-containing dicarboxylic acid, with: (a) adiol represented by formula (2),HO—R¹—OH   (2) wherein R¹ represents an organic group that has a valenceof at least two and that contains at least one selected from the groupconsisting of aliphatic rings, aromatic rings, condensed polycyclicaromatic rings, and heterocycles, to yield a polymer compoundrepresented by formula (6),

(b) a diamine represented by formula (3),H₂N—R²—NH₂   (3) wherein R² represents an organic group that has avalence of at least two and that contains at least one selected from thegroup consisting of aliphatic rings, aromatic rings, condensedpolycyclic aromatic rings, and heterocycles, to yield a polymer compoundrepresented by formula (7),

(c) a diaminodiol represented by formula (4),

wherein R³ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles, to yield a polymer compound represented by formula(8),

or (d) a diaminodiol represented by formula (5),

wherein R⁴ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles, to yield a polymer compound represented by formula(10),

and optionally subjecting a polymer of formula (8) to a dehydration,ring-closing reaction to yield a polymer compound represented by formula(9),

or optionally subjecting a polymer of formula (10) to a dehydration,ring-closing reaction to yield a polymer compound is represented byformula (11),

wherein in formulas (6), (7), (8), (9), (10) and (11); n is defined asabove; R¹, R², R³ and R⁴ are defined as above and may each containfluorine, chlorine, oxygen, sulfur or nitrogen, and a part of hydrogenatoms of R¹, R², R³ and R⁴ may be replaced with an alkyl group,fluoroalkyl group, carboxyl group, hydroxy group, or cyano group; thetwo —CO groups are not adjacent to each other on the aromatic ring, andm represents a positive integer.
 2. A polymer compound according toclaim 1, obtained by reacting a fluorine-containing dicarboxylic acidrepresented by formula (1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring, or an ester-formingderivative of the fluorine-containing dicarboxylic acid, with a diolrepresented by formula (2),HO—R¹—OH   (2) wherein R¹ represents an organic group that has a valenceof at least two and that contains at least one selected from the groupconsisting of aliphatic rings, aromatic rings, condensed polycyclicaromatic rings, and heterocycles, R¹ may contain fluorine, chlorine,oxygen, sulfur or nitrogen, a part of hydrogen atoms of R¹ may bereplaced with an alkyl group, fluoroalkyl group, carboxyl group, hydroxygroup, or cyano group, wherein the polymer compound is represented byformula (6),

wherein n and R¹ are defined as above, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger.
 3. A polymer compound according to claim 1, obtained byreacting a fluorine-containing dicarboxylic acid represented by formula(1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring, or an amide-formingderivative of the fluorine-containing dicarboxylic acid, with a diaminerepresented by formula (3),H₂N—R²—NH₂   (3) wherein R² represents an organic group that has avalence of at least two and that contains at least one selected from thegroup consisting of aliphatic rings, aromatic rings, condensedpolycyclic aromatic rings, and heterocycles, R² may contain fluorine,chlorine, oxygen, sulfur or nitrogen, a part of hydrogen atoms of R² maybe replaced with an alkyl group, fluoroalkyl group, carboxyl group,hydroxy group, or cyano group, wherein the polymer compound isrepresented by formula (7),

wherein n and R² are defined as above, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger.
 4. A polymer compound according to claim 1, obtained byreacting a fluorine-containing dicarboxylic acid represented by formula(1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring, or an amide-formingderivative of the fluorine-containing dicarboxylic acid, with adiaminodiol represented by formula (4),

wherein R³ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles, R³ may contain fluorine, chlorine, oxygen, sulfur ornitrogen, a part of hydrogen atoms of R³ may be replaced with an alkylgroup, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group,wherein the polymer compound is represented by formula (8),

wherein n and R³ are defined as above, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger.
 5. A polymer compound according to claim 1, obtained byreacting a fluorine-containing dicarboxylic acid represented by formula(1),

wherein n represents an integer of 1-4, and the two carboxylic groupsare not adjacent to each other on the aromatic ring, or an amide-formingderivative of the fluorine-containing dicarboxylic acid, with adiaminodiol represented by formula (5),

wherein R⁴ represents an organic group that has a valence of at leastfour and that contains at least one selected from the group consistingof aliphatic rings, aromatic rings, condensed polycyclic aromatic rings,and heterocycles, R⁴ may contain fluorine, chlorine, oxygen, sulfur ornitrogen, a part of hydrogen atoms of R⁴ may be replaced with an alkylgroup, fluoroalkyl group, carboxyl group, hydroxy group, or cyano group,wherein the polymer compound is represented by formula (10),

wherein n and R⁴ are defined as above, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger.
 6. A polymer compound according to claim 1, obtained by adehydration, ring-closing reaction of a polymer compound represented byformula (8),

wherein n represents an integer of 1-4, R³ represents an organic groupthat has a valence of at least four and that contains at least oneselected from the group consisting of aliphatic rings, aromatic rings,condensed polycyclic aromatic rings, and heterocycles, R³ may containfluorine, chlorine, oxygen, sulfur or nitrogen, a part of hydrogen atomsof R³ may be replaced with an alkyl group, fluoroalkyl group, carboxylgroup, hydroxy group, or cyano group, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger, wherein the polymer compound is represented by formula (9),

wherein n, R³ and m are defined as above, and a main chain of thepolymer compound is not bonded to adjacent positions on the aromaticring.
 7. A polymer compound according to claim 1, obtained by adehydration, ring-closing reaction of a polymer compound represented byformula (10),

wherein n represents an integer of 1-4, R⁴ represents an organic groupthat has a valence of at least four and that contains at least oneselected from the group consisting of aliphatic rings, aromatic rings,condensed polycyclic aromatic rings, and heterocycles, R⁴ may containfluorine, chlorine, oxygen, sulfur or nitrogen, a part of hydrogen atomsof R⁴ may be replaced with an alkyl group, fluoroalkyl group, carboxylgroup, hydroxy group, or cyano group, the two —CO groups are notadjacent to each other on the aromatic ring, and m represents a positiveinteger, wherein the polymer compound is represented by formula (11),

wherein n, R⁴ and m are defined as above, and a main chain of thepolymer compound is not bonded to adjacent positions on the aromaticring.